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Milos Toth is a Professor in the School of Mathematical and Physical Sciences. He received a PhD in 2001 from UTS where he worked on the luminescence properties and defect structure of wide bandgap semiconductors.

He subsequently worked as a postdoctoral researcher at Cavendish Laboratory, University of Cambridge, a research scientist at FEI Company laboratories in Boston, Massachusetts and Portland, Oregon (USA). His work in industry was focused on the research and development of charged particle beam nanofabrication and imaging techniques.

Milos returned to UTS in 2011 to take up a Professorial Chair, and to set up a research group focused on electron and ion beam nanofabrication techniques.

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Hexagonal boron nitride (hBN) is an emerging layered material that plays a key role in a variety of two-dimensional devices, and has potential applications in nanophotonics and nanomechanics. Here, we demonstrate the first cavity optomechanical system incorporating hBN. Nanomechanical resonators consisting of hBN beams with average dimensions of 12 m × 1.2 m × 28 nm and minimum predicted thickness of 8 nm were fabricated using electron beam induced etching and positioned in the optical near-field of silicon microdisk cavities. Of the multiple devices studied here a maximum 0.16 pm/[Formula: see text] sensitivity to the hBN nanobeam motion is demonstrated, allowing observation of thermally driven mechanical resonances with frequencies between 1 and 23 MHz, and largest mechanical quality factor of 1100 for a 23 MHz mode, at room temperature in high vacuum. In addition, the role of air damping is studied via pressure dependent measurements. Our results constitute an important step toward realizing integrated optomechanical circuits employing hBN.

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Quantum technologies require robust and photostable single photon emitters (SPEs). Hexagonal boron nitride (hBN) has recently emerged as a promising candidate to host bright and optically stable SPEs operating at room temperature. However, the emission wavelength of the fluorescent defects in hBN has, to date, been shown to be uncontrolled, with a widespread of zero phonon line (ZPL) energies spanning a broad spectral range (hundreds of nanometers), which hinders the potential development of hBN-based devices and applications. Here we demonstrate chemical vapor deposition growth of large-area, few-layer hBN films that host large quantities of SPEs: 100-200 per 10 × 10 m2. More than 85% of the emitters have a ZPL at (580 ± 10) nm, a distribution that is an order of magnitude narrower than reported previously. Furthermore, we demonstrate tuning of the ZPL wavelength using ionic liquid devices over a spectral range of up to 15 nm-the largest obtained to date from any solid-state SPE. The fabricated devices illustrate the potential of hBN for the development of hybrid quantum nanophotonic and optoelectronic devices based on two-dimensional materials.

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Layered van der Waals materials are emerging as compelling two-dimensional platforms for nanophotonics, polaritonics, valleytronics and spintronics, and have the potential to transform applications in sensing, imaging and quantum information processing. Among these, hexagonal boron nitride (hBN) is known to host ultra-bright, room-temperature quantum emitters, whose nature is yet to be fully understood. Here we present a set of measurements that give unique insight into the photophysical properties and level structure of hBN quantum emitters. Specifically, we report the existence of a class of hBN quantum emitters with a fast-decaying intermediate and a long-lived metastable state accessible from the first excited electronic state. Furthermore, by means of a two-laser repumping scheme, we show an enhanced photoluminescence and emission intensity, which can be utilized to realize a new modality of far-field super-resolution imaging. Our findings expand current understanding of quantum emitters in hBN and show new potential ways of harnessing their nonlinear optical properties in sub-diffraction nanoscopy.

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Development of scalable quantum photonic technologies requires on-chip integration of photonic components. Recently, hexagonal boron nitride (hBN) has emerged as a promising platform, following reports of hyperbolic phonon-polaritons and optically stable, ultra-bright quantum emitters. However, exploitation of hBN in scalable, on-chip nanophotonic circuits and cavity quantum electrodynamics (QED) experiments requires robust techniques for the fabrication of high-quality optical resonators. In this letter, we design and engineer suspended photonic crystal cavities from hBN and demonstrate quality (Q) factors in excess of 2000. Subsequently, we show deterministic, iterative tuning of individual cavities by direct-write EBIE without significant degradation of the Q-factor. The demonstration of tunable cavities made from hBN is an unprecedented advance in nanophotonics based on van der Waals materials. Our results and hBN processing methods open up promising avenues for solid-state systems with applications in integrated quantum photonics, polaritonics and cavity QED experiments.

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We propose and design photonic crystal cavities (PCCs) in hexagonal boron nitride (hBN) for diverse photonic and quantum applications. Two dimensional (2D) hBN flakes contain quantum emitters which are ultra-bright and photostable at room temperature. To achieve optimal coupling of these emitters to optical resonators, fabrication of cavities from hBN is therefore required to maximize the overlap between cavity optical modes and the emitters. Here, we design 2D and 1D PCCs using anisotropic indices of hBN. The influence of underlying substrates and material absorption are investigated, and spontaneous emission rate enhancements are calculated. Our results are promising for future quantum photonic experiments with hBN.

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Multiphoton fluorescence microscopy (MPM), using near infrared excitation light, provides increased penetration depth, decreased detection background, and reduced phototoxicity. Using stimulated emission depletion (STED) approach, MPM can bypass the diffraction limitation, but it requires both spatial alignment and temporal synchronization of high power (femtosecond) lasers, which is limited by the inefficiency of the probes. Here, we report that upconversion nanoparticles (UCNPs) can unlock a new mode of near-infrared emission saturation (NIRES) nanoscopy for deep tissue super-resolution imaging with excitation intensity several orders of magnitude lower than that required by conventional MPM dyes. Using a doughnut beam excitation from a 980nm diode laser and detecting at 800nm, we achieve a resolution of sub 50nm, 1/20th of the excitation wavelength, in imaging of single UCNP through 93m thick liver tissue. This method offers a simple solution for deep tissue super resolution imaging and single molecule tracking.

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Single crystal, nanoscale diamond membranes are highly sought after for a variety of applications including nanophotonics, nanoelectronics and quantum information science. However, so far, the availability of conductive diamond membranes has remained an unreachable goal. In this work we present a complete nanofabrication methodology for engineering high aspect ratio, electrically active single crystal diamond membranes. The membranes have large lateral directions, exceeding 500 × 500 m2 and are only several hundreds of nanometers thick. We further realize vertical single crystal p-n junctions made from the diamond membranes that exhibit onset voltages of 10 V and a current of several mA. Moreover, we deterministically introduce optically active color centers into the membranes, and demonstrate for the first time a single crystal nanoscale diamond LED. The robust and scalable approach to engineer the electrically active single crystal diamond membranes offers new pathways for advanced nanophotonic, nanoelectronic and optomechanical devices employing diamond.

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Synthesis of Co9S8, Ni3S2, Co and Ni nanowires by solventless thermolysis of a mixture of metal(ii) acetate and cysteine in vacuum is reported. The simple precursor system enables the nanowire phase to be tuned from pure metal (Co or Ni) to metal sulfide (Co9S8, Ni3S2) by varying the relative concentration of the metal(ii) acetate. The growth environment facilitates new insights through in situ characterization using field-emission scanning electron microscopy (FESEM) and thermogravimetric analysis with gas chromatography-mass spectrometry (TGA-GC-MS). Direct observation by FESEM shows the temperature at which nanowire growth occurs and suggests adatoms are incorporated into the base of the growing nanowire. TGA-GC-MS reveals the rates of precursor decomposition and identity of the volatilized ligand fragments during heat-up and at the nanowire growth temperature. Our results constitute a new approach for the selective fabrication of high quality Co9S8 and Ni3S2 nanowires and more importantly provides new understanding of precursor decomposition reactions that support symmetry-breaking growth in nanocrystals by heat-up synthesis.

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Layered van der Waals materials are emerging as compelling two-dimensional platforms for nanophotonics, polaritonics, valleytronics and spintronics, and have the potential to transform applications in sensing, imaging and quantum information processing. Among these, hexagonal boron nitride (hBN) is known to host ultra-bright, room-temperature quantum emitters, whose nature is yet to be fully understood. Here we present a set of measurements that give unique insight into the photophysical properties and level structure of hBN quantum emitters. Specifically, we report the existence of a class of hBN quantum emitters with a fast-decaying intermediate and a long-lived metastable state accessible from the first excited electronic state. Furthermore, by means of a two-laser repumping scheme, we show an enhanced photoluminescence and emission intensity, which can be utilized to realize a new modality of far-field super-resolution imaging. Our findings expand current understanding of quantum emitters in hBN and show new potential ways of harnessing their nonlinear optical properties in sub-diffraction nanoscopy.

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Hexagonal boron nitride (hBN) mono and multilayers are promising hosts for room-temperature single photon emitters (SPEs). In this work we explore high-energy (MeV) electron irradiation as a means to generate stable SPEs in hBN. We investigate four types of exfoliated hBN flakes-namely, high-purity multilayers, isotopically pure hBN, carbon-rich hBN multilayers and monolayered material-and find that electron irradiation increases emitter concentrations dramatically in all samples. Furthermore, the engineered emitters are located throughout hBN flakes (not only at flake edges or grain boundaries) and do not require activation by high-temperature annealing of the host material after electron exposure. Our results provide important insights into controlled formation of hBN SPEs and may aid in identification of their crystallographic origin.

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The assembly of quantum nanophotonic systems with plasmonic resonators is important for fundamental studies of single photon sources as well as for on-chip information processing. In this work, we demonstrate the controllable nanoassembly of gold nanospheres with ultra-bright narrow-band quantum emitters in 2D layered hexagonal boron nitride (hBN). We utilize an atomic force microscope (AFM) tip to precisely position gold nanospheres to close proximity to the quantum emitters and observe the resulting emission enhancement and fluorescence lifetime reduction. The extreme emitter photostability permits analysis at high excitation powers, and delineation of absorption and emission enhancement caused by the plasmonic resonators. A fluorescence enhancement of over 300% is achieved experimentally for quantum emitters in hBN, with a radiative quantum efficiency of up to 40% and a saturated count rate in excess of 5 × 106 counts per s. Our results are promising for the future employment of quantum emitters in hBN for integrated nanophotonic devices and plasmonic based nanosensors.

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Artificial atomic systems in solids are becoming increasingly important building blocks in quantum information processing and scalable quantum nanophotonic networks. Amongst numerous candidates, 2D hexagonal boron nitride has recently emerged as a promising platform hosting single photon emitters. Here, we report a number of robust plasma and thermal annealing methods for fabrication of emitters in tape-exfoliated hexagonal boron nitride (hBN) crystals. A two-step process comprising Ar plasma etching and subsequent annealing in Ar is highly robust, and yields an eight-fold increase in the concentration of emitters in hBN. The initial plasma-etching step generates emitters that suffer from blinking and bleaching, whereas the two-step process yields emitters that are photostable at room temperature with emission wavelengths greater than 700 nm. Density functional theory modeling suggests that the emitters might be associated with defect complexes that contain oxygen. This is further confirmed by generating the emitters via annealing hBN in air. Our findings advance the present understanding of the structure of quantum emitters in hBN and enhance the nanofabrication toolkit needed to realize integrated quantum nanophotonic circuits.

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Diamond is an ideal material for a broad range of current and emerging applications in tribology, quantum photonics, high-power electronics, and sensing. However, top-down processing is very challenging due to its extreme chemical and physical properties. Gas-mediated electron beam-induced etching (EBIE) has recently emerged as a minimally invasive, facile means to dry etch and pattern diamond at the nanoscale using oxidizing precursor gases such as O2 and H2O. Here we explain the roles of oxygen and hydrogen in the etch process and show that oxygen gives rise to rapid, isotropic etching, while the addition of hydrogen gives rise to anisotropic etching and the formation of topographic surface patterns. We identify the etch reaction pathways and show that the anisotropy is caused by preferential passivation of specific crystal planes. The anisotropy can be controlled by the partial pressure of hydrogen and by using a remote RF plasma source to radicalize the precursor gas. It can be used to manipulate the geometries of topographic surface patterns as well as nano- and microstructures fabricated by EBIE. Our findings constitute a comprehensive explanation of the anisotropic etch process and advance present understanding of electron-surface interactions.

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Under ambient conditions and in H2O and O2 environments, reactive oxygen species (ROS) cause immediate degradation of the mobility of few-layer black phosphorus (FLBP). Here, we show that FLBP degradation can be prevented by maintaining the temperature in the range 125-300 °C during ROS exposure. FLBP devices maintained at elevated temperature show no deterioration of electrical conductance, in contrast to the immediate degradation of pristine FLBP held at room temperature. Our results constitute the first demonstration of stable FLBP in the presence of ROS without requiring encapsulation or a protective coating. The stabilization method will enable applications based on the surface properties of intrinsic FLBP.

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Collective behavior of bacterial colonies plays critical roles in adaptability, survivability, biofilm expansion and infection. We employ an individual-based model of an interstitial biofilm to study emergent pattern formation based on the assumptions that rod-shaped bacteria furrow through a viscous environment and excrete extracellular polymeric substances which bias their rate of motion. Because the bacteria furrow through their environment, the substratum stiffness is a key control parameter behind the formation of distinct morphological patterns. By systematically varying this property (which we quantify with a stiffness coefficient ), we show that subtle changes in the substratum stiffness can give rise to a stable state characterized by a high degree of local order and long-range pattern formation. The ordered state exhibits characteristics typically associated with bacterial fitness advantages, even though it is induced by changes in environmental conditions rather than changes in biological parameters. Our findings are applicable to a broad range of biofilms and provide insights into the relationship between bacterial movement and their environment, and basic mechanisms behind self-organization of biophysical systems.

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Room-temperature quantum emitters in gallium nitride (GaN) are reported. The emitters originate from cubic inclusions in hexagonal lattice and exhibit narrowband luminescence in the red spectral range. The sources are found in different GaN substrates, and therefore are promising for scalable quantum technologies.

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Hexagonal boron nitride (hBN) has recently emerged as a fascinating platform for room-temperature quantum photonics due to the discovery of robust visible light single-photon emitters. In order to utilize these emitters, it is necessary to have a clear understanding of their atomic structure and the associated excitation processes that give rise to this single photon emission. Here, we performed density-functional theory (DFT) and constrained DFT calculations for a range of hBN point defects in order to identify potential emission candidates. By applying a number of criteria on the electronic structure of the ground state and the atomic structure of the excited states of the considered defects, and then calculating the Huang-Rhys (HR) factor, we found that the CBVN defect, in which a carbon atom substitutes a boron atom and the opposite nitrogen atom is removed, is a potential emission source with a HR factor of 1.66, in good agreement with the experimental HR factor. We calculated the photoluminescence (PL) line shape for this defect and found that it reproduces a number of key features in the experimental PL lineshape.

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Anisotropic collective patterns occur frequently in the morphogenesis of two-dimensional biofilms. These patterns are often attributed to growth regulation mechanisms and differentiation based on gradients of diffusing nutrients and signaling molecules. Here, we employ a model of bacterial growth dynamics to show that even in the absence of growth regulation or differentiation, confinement by an enclosing medium such as agar can itself lead to stable pattern formation over time scales that are employed in experiments. The underlying mechanism relies on path formation through physical deformation of the enclosing environment.

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Ultra-nanocrystalline diamond (UNCD) is increasingly being used in the fabrication of devices and coatings due to its excellent tribological properties, corrosion resistance, and biocompatibility. Here, we study its response to irradiation with kiloelectronvolt electrons as a controlled model for extreme ionizing environments. Real time Raman spectroscopy reveals that the radiation-damage mechanism entails dehydrogenation of UNCD grain boundaries, and we show that the damage can be recovered by annealing at 883 K. Our results have significant practical implications for the implementation of UNCD in extreme environment applications, and indicate that the films can be used as radiation sensors.

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Quantum emitters in two-dimensional materials are promising candidates for studies of light-matter interaction and next generation, integrated on-chip quantum nanophotonics. However, the realization of integrated nanophotonic systems requires the coupling of emitters to optical cavities and resonators. In this work, we demonstrate hybrid systems in which quantum emitters in 2D hexagonal boron nitride (hBN) are deterministically coupled to high-quality plasmonic nanocavity arrays. The plasmonic nanoparticle arrays offer a high-quality, low-loss cavity in the same spectral range as the quantum emitters in hBN. The coupled emitters exhibit enhanced emission rates and reduced fluorescence lifetimes, consistent with Purcell enhancement in the weak coupling regime. Our results provide the foundation for a versatile approach for achieving scalable, integrated hybrid systems based on low-loss plasmonic nanoparticle arrays and 2D materials.

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Twitching motility is a mode of surface translocation that is mediated by the extension and retraction of type IV pili and which, depending on the conditions, enables migration of individual cells or can manifest as a complex multicellular collective behavior that leads to biofilm expansion. When twitching motility occurs at the interface of an abiotic surface and solidified nutrient media, it can lead to the emergence of extensive self-organized patterns of interconnected trails that form as a consequence of the actively migrating bacteria forging a furrow network in the substratum beneath the expanding biofilm. These furrows appear to direct bacterial movements much in the same way that roads and footpaths coordinate motor vehicle and human pedestrian traffic. Self-organizing systems such as these can be accounted for by the concept of stigmergy which describes self-organization that emerges through indirect communication via persistent signals within the environment. Many bacterial communities are able to actively migrate across solid and semi-solid surfaces through complex multicellular collective behaviors such as twitching motility and flagella-mediated swarming motility. Here, we have examined the potential of exploiting the stigmergic behavior of furrow-mediated trail following as a means of controlling bacterial biofilm expansion along abiotic surfaces. We found that incorporation of a series of parallel micro-fabricated furrows significantly impeded active biofilm expansion by Pseudomonas aeruginosa and Proteus vulgaris. We observed that in both cases bacterial movements tended to be directed along the furrows. We also observed that narrow furrows were most effective at disrupting biofilm expansion as they impeded the ability of cells to self-organize into multicellular assemblies required for escape from the furrows and migration into new territory. Our results suggest that the implementation of micro-fabricated furrows that exploit stigmergy may be a ...

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Few-layer black phosphorous (BP) has emerged as a promising candidate for next-generation nanophotonic and nanoelectronic devices. However, rapid ambient degradation of mechanically exfoliated BP poses challenges in its practical deployment in scalable devices. To date, the strategies employed to protect BP have relied upon preventing its exposure to atmospheric conditions. Here, an approach that allows this sensitive material to remain stable without requiring its isolation from the ambient environment is reported. The method draws inspiration from the unique ability of biological systems to avoid photo-oxidative damage caused by reactive oxygen species. Since BP undergoes similar photo-oxidative degradation, imidazolium-based ionic liquids are employed as quenchers of these damaging species on the BP surface. This chemical sequestration strategy allows BP to remain stable for over 13 weeks, while retaining its key electronic characteristics. This study opens opportunities to practically implement BP and other environmentally sensitive 2D materials for electronic applications.

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Diamond nanocrystals that host room temperature narrowband single photon emitters are highly sought after for applications in nanophotonics and bioimaging. However, current understanding of the origin of these emitters is extremely limited. In this work, we demonstrate that the narrowband emitters are point defects localized at extended morphological defects in individual nanodiamonds. In particular, we show that nanocrystals with defects such as twin boundaries and secondary nucleation sites exhibit narrowband emission that is absent from pristine individual nanocrystals grown under the same conditions. Critically, we prove that the narrowband emission lines vanish when extended defects are removed deterministically using highly localized electron beam induced etching. Our results enhance the current understanding of single photon emitters in diamond and are directly relevant to fabrication of novel quantum optics devices and sensors.

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Artificial atomic systems in solids are widely considered the leading physical system for a variety of quantum technologies, including quantum communications, computing and metrology. To date, however, room-temperature quantum emitters have only been observed in wide-bandgap semiconductors such as diamond and silicon carbide, nanocrystal quantum dots, and most recently in carbon nanotubes. Single-photon emission from two-dimensional materials has been reported, but only at cryogenic temperatures. Here, we demonstrate room-temperature, polarized and ultrabright single-photon emission from a colour centre in two-dimensional hexagonal boron nitride. Density functional theory calculations indicate that vacancy-related defects are a probable source of the emission. Our results demonstrate the unprecedented potential of van der Waals crystals for large-scale nanophotonics and quantum information processing.

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Growth of one-dimensional materials is possible through numerous mechanisms that affect the nanowire structure and morphology. Here, we explain why a wide range of morphologies is observed when silicon oxide nanowires are grown on silicon substrates using liquid gallium catalyst droplets. We show that a gallium oxide overlayer is needed for nanowire nucleation at typical growth temperatures, and that it can decompose during growth and, hence, dramatically alter the nanowire morphology. Gallium oxide decomposition is attributed to etching caused by hydrogen that can be supplied by thermal dissociation of H2O (a common impurity). We show that H2O dissociation is catalyzed by silicon substrates at temperatures as low as 320 °C, identify the material supply pathways and processes that rate-limit nanowire growth under dry and wet atmospheres, and present a detailed growth model that explains contradictory results reported in prior studies. We also show that under wet atmospheres the Ga droplets can be mobile and promote nanowire growth as they traverse the silicon substrate.

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Environmental scanning electron microscopy (ESEM) and environmental photoelectron yield spectroscopy (EPYS) enable electron imaging and spectroscopy of surfaces and interfaces in low vacuum, gaseous environments. The techniques are both appealing and limited by the range of gases that can be used to amplify electrons emitted from a sample, and used to form images/spectra. However, to date, only H2O and NH3 gases have been identified as highly favorable electron amplification media. Here we demonstrate that ethanol vapor (CH3CH2OH) is superior to both of these, and attribute its performance to molecular complexity and valence orbital structure. Our findings improve present understanding of what constitutes a favorable electron amplification gas, and will help expand the applicability and usefulness of the ESEM and EPYS techniques.

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Metal and metal alloy nanowires have applications ranging from spintronics to drug delivery, but high quality, high density single crystalline materials have been surprisingly difficult to fabricate. Here we report a versatile, template-free, self-assembly method for fabrication of single crystalline metal and metal alloy nanowires (Co, Ni, NiCo, CoFe, and NiFe) by reduction of metal nitride precursors formed in situ by reaction of metal salts with a nitrogen source. Thiol reduction of the metal nitrides to the metallic phase at 550-600 °C results in nanowire growth. In this process, sulfur acts as a uniaxial structure-directing agent, passivating the surface of the growing nanowires and preventing radial growth. The versatility of the method is demonstrated by achieving nanowire growth from gas-phase, solution-phase or a combination of gas- and solution-phase precursors. The fabrication method is suited to large-area CVD on a wide range of solid substrates.

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Hexagonal boron nitride (hBN) is a wide bandgap van der Waals material with unique optical properties that make it attractive for two dimensional (2D) photonic and optoelectronic devices. However, broad deployment and exploitation of hBN is limited by alack of suitable material and device processing and nano prototyping techniques. Here we present a high resolution, single step electron beam technique for chemical dry etching of hBN. Etching is achieved using H2O as a precursor gas, at both room temperature and elevated hBN temperatures. The technique enables damage-free, nano scale, iterative patterning of supported and suspended 2D hBN, thus opening the door to facile fabrication of hBN-based 2D heterostructures and devices.

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Hexagonal boron nitride (hBN) is an emerging two-dimensional material for quantum photonics owing to its large bandgap and hyperbolic properties. Here we report two approaches for engineering quantum emitters in hBN multilayers using either electron beam irradiation or annealing and characterize their photophysical properties. The defects exhibit a broad range of multicolor room-temperature single photon emissions across the visible and the near-infrared spectral ranges, narrow line widths of sub-10 nm at room temperature, and a short excited-state lifetime, and high brightness. We show that the emitters can be categorized into two general groups, but most likely possess similar crystallographic structure. Remarkably, the emitters are extremely robust and withstand aggressive annealing treatments in oxidizing and reducing environments. Our results constitute a step toward deterministic engineering of single emitters in 2D materials and hold great promise for the use of defects in boron nitride as sources for quantum information processing and nanophotonics.

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Arrays of fluorescent nanoparticles are highly sought after for applications in sensing, nanophotonics and quantum communications. Here we present a simple and robust method of assembling fluorescent nanodiamonds into macroscopic arrays. Remarkably, the yield of this directed assembly process is greater than 90% and the assembled patterns withstand ultra-sonication for more than three hours. The assembly process is based on covalent bonding of carboxyl to amine functional carbon seeds and is applicable to any material, and to non-planar surfaces. Our results pave the way to directed assembly of sensors and nanophotonics devices.

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We report highly ordered topographic patterns that form on the surface of diamond, span multiple length scales, and have a symmetry controlled by the precursor gas species used in electron-beam-induced etching (EBIE). The pattern formation dynamics reveals an etch rate anisotropy and an electron energy transfer pathway that is overlooked by existing EBIE models. We, therefore, modify established theory such that it explains our results and remains universally applicable to EBIE. The patterns can be exploited in controlled wetting, optical structuring, and other emerging applications that require nano- and microscale surface texturing of a wide band-gap material.

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A facile and cost-effective self-assembly route to engineering of vital quantum plasmonic circuit components is reported. By modifying the surface energy of silver nanowires, the position and density of attached nanodiamonds can be maneuvered leading to silver nanowire/nanodiamond(s) hybrid nanostructures. These structures exhibit strong plasmonic coupling effects and thus hold promise to serve as quantum plasmonic components.

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Electron-beam-induced deposition (EBID) is a direct-write chemical vapor deposition technique in which an electron beam is used for precursor dissociation. Here we show that Arrhenius analysis of the deposition rates of nanostructures grown by EBID can be used to deduce the diffusion energies and corresponding preexponential factors of EBID precursor molecules. We explain the limitations of this approach, define growth conditions needed to minimize errors, and explain why the errors increase systematically as EBID parameters diverge from ideal growth conditions. Under suitable deposition conditions, EBID can be used as a localized technique for analysis of adsorption barriers and prefactors.

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Cryogenic cooling is used to enable efficient, gas-mediated electron beam induced etching (EBIE) in cases where the etch rate is negligible at room and elevated substrate temperatures. The process is demonstrated using nitrogen trifluoride (NF3) as the etch precursor, and Si, SiO2, SiC, and Si3N4 as the materials volatilized by an electron beam. Cryogenic cooling broadens the range of precursors that can be used for EBIE, and enables high-resolution, deterministic etching of materials that are volatilized spontaneously by conventional etch precursors as demonstrated here by NF3 and XeF2 EBIE of silicon.

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Gas-mediated electron beam induced etching (EBIE) is a nanoscale, direct-write technique analogous to gas-assisted focused ion beam (FIB) milling. The main advantage of EBIE is the elimination of sputtering and ion implantation during processing as well as greater material selectivity [1]. Here we discuss recent developments that expand the scope of EBIE applications in nanofabrication and defect generation analysis, and show advances in hardware that open the door for new studies in reaction kinetics using a scanning electron microscope (SEM).

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Direct-write three-dimensional nanolithography is demonstrated using cryogenic electron beam-induced deposition (EBID). Cryogenic cooling and an electron beam were used to condense and expose the precursor methylcyclopentadienyl(trimethyl) platinum (MeCp

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We report a new mechanism that limits the rate of electron beam induced etching (EBIE). Typically, the etch rate is assumed to scale directly with the precursor adsorbate dissociation rate. Here, we show that this is a special case, and that the rate can instead be limited by the concentration of active sites at the surface. Novel etch kinetics are expected if surface sites are activated during EBIE, and observed experimentally using the electron sensitive material ultra nanocrystalline diamond (UNCD). In practice, etch kinetics are of interest because they affect resolution, throughput, proximity effects, and the topography of nanostructures and nanostructured devices fabricated by EBIE.

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Nanocrystalline platinum is synthesized at room temperature by co-injecting Pt(PF3)4 and XeF2 vapors onto solid supports in vacuum. The Pt nucleation time scales with chemisorbed fluorine coverage, which is controlled by pre-dosing supports with XeF2, and by optional electron or ion beam irradiation under flowing XeF2. The latter is used to increase the chemisorbed fluorine coverage and localize the Pt growth process.

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Gold coated borosilicate nanocapillaries are used to locally deliver aqueous, electrolytic CuSO4 solution into the low vacuum chamber of an environmental scanning electron microscope (ESEM). Capillary flow of the liquid is induced by bringing a nanocapil

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Electron beam induced deposition (EBID) is limited by low throughput and purity of as-grown material. Co-injection of O2 with the growth precursor is known to increase both the purity and deposition rate of materials such as SiO2 at room temperature. Here, we show that O2 inhibits rather than enhances EBID from tetraethoxysilane (TEOS) precursor at elevated temperatures. This behavior is attributed to surface site competition between chemisorbates at elevated temperature, and TEOS decomposition by atomic oxygen produced through electron dissociation of physisorbed O2 at room temperature.

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Models of adsorbate dissociation by energetic electrons are generalized to account for activated sticking and chemisorption, and used to simulate the rate kinetics of electron beam induced chemical vapor deposition (EBID). The model predicts a novel temperature dependence caused by thermal transitions from physisorbed to chemisorbed states that govern adsorbate coverage and EBID rates at elevated temperatures. We verify these results by experiments that also show how EBID can be used to deposit high purity materials and characterize the rates and energy barriers that govern adsorption.

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We report the use of ammonia (NH3) vapor as a new precursor for nanoscale electron beam induced etching (EBIE) of carbon, and an efficient imaging medium for environmental scanning electron microscopy (ESEM). Etching is demonstrated using amorphous carbonaceous nanowires grown by electron beam induced deposition (EBID). It is ascribed to carbon volatilization by hydrogen radicals generated by electron dissociation of NH3 adsorbates. The volatilization process is also effective at preventing the buildup of residual hydrocarbon impurities that often compromise EBIE, EBID and electron imaging. We also show that ammonia is a more efficient electron imaging medium than H2O, which up to now has been the most commonly used ESEM imaging gas.

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Direct-write, cryogenic electron beam-induced deposition (EBID) was performed by condensing methylcyclopentadienyl-platinum-trimethyl precursor onto a substrate at 155 °C, exposing the condensate by a 15 keV electron beam, and desorbing unexposed precursor molecules by heating the substrate to room temperature. Dependencies of film thickness, microstructure, and surface morphology on electron beam flux and fluence, and Monte Carlo simulations of electron interactions with the condensate are used to construct a model of cryogenic EBID that is contrasted to existing models of conventional, room temperature EBID. It is shown that material grown from a cryogenic condensate exhibits one of three distinct surface morphologies: a nanoporous mesh with a high surface-to-volume ratio; a smooth, continuous film analogous to material typically grown by room temperature EBID; or a film with a high degree of surface roughness, analogous to that of the cryogenic condensate. The surface morphology can be controlled reproducibly by the electron fluence used for exposure.

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Electron beam induced etching (EBIE) is a high resolution, direct write, chemical dry etch process in which surface-adsorbed precursor molecules are activated by an electron beam. We show that nanoscale EBIE is rate limited through at least two mechanisms ascribed to adsorbate depletion and the transport of gaseous precursor molecules into an etch pit during etching, respectively. The latter has, to date, not been accounted for in models of EBIE and is needed to reproduce etch kinetics which govern the time-evolution of etch pits, EBIE throughput, and spatial resolution.

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We describe a feedback mechanism in the gas cascade amplification process used in magnetic immersion lens environmental scanning electron microcopy (ESEM). Feedback dominates gas gain under the conditions typically used for ultra-high-resolution ESEM and gives rise to novel dependencies of the imaging signal and noise on microscope operating parameters. It is ascribed tentatively to the generation of free electrons upon de-excitation of metastable species in the gas cascade. The results have implications for optimization of ESEM systems for applications such as critical dimension metrology and real-time imaging of nanostructure growth by gas mediated electron beam induced deposition.

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The noise characteristics of gas cascade amplified electron signals in low vacuum scanning electron microscopy (LVSEM) are described and analyzed. We derive expressions for each component contributing to the total noise culminating in a predictive, quantitative model that can be used for optimization of LVSEM operating parameters. Signal and noise behavior is characterized experimentally and used to validate the model. Under most operating conditions, the noise is dominated by the excess noise generated in the gas amplification cascade. At high gains, the excess noise increases proportionally with gain such that the signal-to-noise ratio is constant. The effects of several instrument operating parameters, including working distance, gas pressure, beam current, and detector bias, are condensed and presented in the form of a master curve.

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The material grown in a scanning electron microscope by electron beam-induced deposition (EBID) using Pt(PF3)4 precursor is shown to be electron beam sensitive. The effects of deposition time and postgrowth electron irradiation on the microstructure and resistivity of the deposits were assessed by transmission electron microscopy, selected area diffraction, and four-point probe resistivity measurements. The microstructure, notably the platinum nanocrystallite grain size, is shown to evolve with electron fluence in a controllable manner. The resistivity was observed to decrease as a result of postgrowth electron irradiation, with the lowest observed value of 215±15 µO?cm. The authors demonstrate that electron beam-induced changes in microstructure can be caused using electron fluences similar to those used during the course of EBID and suggest that the observed effects can be used to tailor the microstructure and functionality of deposits grown by EBID in situ without breaking vacuum.

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Many ultraviolet, x-ray and charged particle beam techniques are inhibited by the growth of carbonaceous films caused by cross linking of hydrocarbon contaminant adsorbates. In electron microscopy, such films obscure surface features and reduce resolution. We demonstrate how resolution degradation can be alleviated using a H2O environment via gas mediated, electron beam induced carbon volatilization, a process that competes with film growth. Net behavior is a function of electron flux, which provides control over growth kinetics during imaging. Under optimized conditions, film growth can be eliminated, removing contamination as a factor limiting image information content and resolution.

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Environmental scanning electron microscopy (ESEM) was used to perform electron beam induced deposition (EBID) using a WF6 precursor. The deposits consist of WO3 nanocrystals embedded in an amorphous matrix. Oxide formation is attributed to residual oxidizers present in the ESEM chamber during EBID. Under conditions of fixed low electron flux, the WO3 grain size and the degree of deposit crystallinity increase with time. These changes correlate with the degree of electron energy deposition into the material during growth, indicating that electron beam induced modification of as-grown material is significant in controlling the nanostructure and functionality of materials fabricated by EBID. (C) 2008 American Institute of Physics.

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Aerogels (AGs) are ultralow-density nanoporous solids that have numerous potential applications. However, as most AGs are strong insulators with poor mechanical properties, direct studies of the complex nanoporous structure of AGs by methods such as atomic force and conventional scanning electron microscopy (SEM) have not proven feasible. Here, we use low-vacuum SEM to image directly the ligament and pore size and shape distributions of representative AGs over a wide range of length scales (similar to 10(0)-10(5) nm). The structural information obtained is used for unambiguous, real-space interpretation of small-angle X-ray scattering curves for these complex nanoporous systems. Low-vacuum SEM permits imaging of both cross-sections and skin layers of AG monoliths. Images of skin layers reveal the presence of microcracks, which alter the properties of cast monolithic AGs.

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Electron beam induced deposition (EBID) and etching (EBIE) are promising methods for the fabrication of three-dimensional nanodevices, wiring of nanostructures, and repair of photolithographic masks. Here, we study simultaneous EBID and EBIE, and demonstrate an athermal electron flux controlled transition between material deposition and etching. The switching is observed when one of the processes has both a higher efficiency and a lower precursor partial pressure than the other. This is demonstrated in two technologically important systems: during XeF2-mediated etching of chrome on a photolithographic mask and during deposition and etching of carbonaceous films on a semiconductor surface. Simultaneous EBID and EBIE can be used to enhance the spatial localization of etch profiles. It plays a key role in reducing contamination buildup rates during low vacuum electron imaging and deposition of high purity nanostructures in the presence of oxygen-containing gases. (c) 2007 American Institute of Physics.

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Electron beam induced deposition (EBID) is a maskless nanofabrication technique capable of surpassing the resolution limits of resist-based lithography. However, EBID fabrication of functional nanostructures is limited by beam spread in bulk substrates, substrate charging, and delocalized film growth around deposits. Here, we overcome these problems by using environmental scanning electron microscopy (ESEM) to perform EBID and etching while eliminating charging artifacts at the nanoscale. Nanostructure morphology is tailored by slimming of deposits by ESEM imaging in the presence of a gaseous etch precursor and by pre-etching small features into a deposit (using a stationary or a scanned electron beam) prior to a final imaging process. The utility of this process is demonstrated by slimming of nanowires deposited by EBID, by the fabrication of gaps (between 4 and 7 nm wide) in the wires, and by the removal of thin films surrounding such nanowires. ESEM imaging provides a direct view of the slimming process, yielding process resolution that is limited by ESEM image resolution (similar to 1 nm) and surface roughening occurring during etching.

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Cathodoluminescence (CL) spectra from silicon doped and undoped wurtzite n-type GaN have been measured in a SEM under a wide range of electron beam excitation conditions, which include accelerating voltage, beam current, magnification, beam diameter, and specimen temperature. The CL intensity dependence on excitation density was analyzed using a power-law model (ICL [is proportional to] Jm) for each of the observed CL bands in this material. The yellow luminescence band present in both silicon and undoped GaN exhibits a close to cube root (m = 0.33) dependence on electron beam excitation at both 77 K and 300 K. However, the blue (at 300 K) and donor-acceptor pair (at 77 K) emission peaks observed in undoped GaN follow power laws with exponents of m = 1 and m = 0.5, respectively. As expected from its excitonic character, the near band edge emission intensity depends linearly (m = 1) in silicon doped GaN and superlinearly (m = 1.2) in undoped GaN on the electron beam current. Results show that the intensities of the CL bands are highly dependent not only on the defect concentration but also on the electron-hole pair density and injection rate. Furthermore, the size of the focussed electron beam was found to have a considerable effect on the relative intensities of the CL emission peaks. Hence SEM parameters such as the objective lens aperture size, astigmatism, and the condenser lens setting must also be considered when assessing CL data based on intensity measurements from this material.

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Electrical isolation of n-type GaN epilayers bombarded with MeV light ions is studied by energy dispersive x-ray spectrometry (EDS). We show that the maximum bremsstrahlung x-ray energy (the Duane-Hunt limit) can be used to monitor the isolation process in GaN. This method allows the dose region above the threshold dose for isolation to be conveniently studied, whereas the application of conventional (low-voltage) electrical techniques in this dose range with large sheet resistances of the material (>~1011 ?/sq) is often impossible due to comparable parasitic resistances of the experimental setup. A correlation of EDS and resistance measurements of GaN strongly suggests that the magnitude of sample charging scales with the number of ion-beam-produced deep electron traps which are empty at equilibrium. The results presented demonstrate the utility of EDS as a powerful and simple technique to study electrical isolation in wide band-gap semiconductors.

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The influence of ion-beam-produced lattice defects as well as H, B, C, N, O, and Si, introduced by ion implantation, on the luminescence properties of wurtzite GaN is studied by cathodoluminescence spectroscopy. Results indicate that intrinsic lattice defects produced by ion bombardment mainly act as nonradiative recombination centers and do not give rise to the yellow luminescence (YL) of GaN. Experimental data unequivocally shows that C is involved in the defect-impurity complex responsible for YL. In addition, C-related complexes appear to act as efficient nonradiative recombination centers. Implantation of H produces a broad luminescent peak which is slightly blueshifted with respect to the C-related YL band in the case of high excitation densities. The position of this H-related YL peak exhibits a blueshift with increasing excitation density. Based on this experimental data and results reported previously, the chemical origin of the YL band is discussed

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We report on the properties of electric fields generated as a result of electron irradiation of dielectrics in a low vacuum scanning electron microscope. Individual field components produced by (i) ionized gas molecules located outside the sample surface and (ii) subsurface trapped charge were detected by measurements of changes in (i) primary electron landing energy and (ii) secondary electron (SE) emission current, respectively. The results provide experimental evidence for a recently proposed model of field-enhanced SE emission from electron irradiated insulators in a low vacuum environment [Toth et al., J. Appl. Phys. 91, 4479 (2002)]. Errors introduced into x-ray microanalysis by the electric fields generated by ionized gas molecules can be alleviated by minimizing the steady state ion concentration by the provision of efficient ion neutralization routes. It is demonstrated how this can be achieved using simple sample-electrode geometries.

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We demonstrate that if charging caused by electron irradiation of an insulator is controlled by a defocused flux of soft-landing positive ions, secondary electron (SE) images can contain contrast due to lateral variations in (i) changes in the SE yield caused by subsurface trapped charge and (ii) the SE-ion recombination rate. Both contrast mechanisms can provide information on microscopic variations in dielectric properties. We present a model of SE contrast formation that accounts for localized charging and the effects of gas ions on the SE emission process, emitted electrons above the sample surface, and subsurface trapped charge. The model explains the ion flux dependence of charge-induced SE contrast, an increase in the sensitivity to surface contrast observed in SE images of charged dielectrics, and yields procedures for identification of contrast produced by localized sample charging.

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Trace levels of Cr impurities in epitaxial GaN grown on sapphire substrates were investigated using cathodoluminescence (CL) spectroscopy. CL emissions characteristic of Cr in an octahedral crystal field were observed from beta-Ga2O3 overlayers produced

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We present a method for imaging depletion layers using the gaseous secondary electron detector (GSED) employed in environmental scanning electron microscopes. GSED images of a p-n junction were obtained from a Si P+PN power diode. Behavior of the junctio

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We present the results of a depth-resolved cathodoluminescence (CL) and transmission electron microscopy study of autodoped GaN grown on sapphire. Depth-resolved CL analysis can be used for depth profiling of the yellow luminescence (YL) center concentra

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We present experimental evidence of electron-beam-induced diffusion of O and H in unintentionally doped n-type GaN grown on a sapphire substrate. Impurity diffusion was investigated using cathodoluminescence kinetics and imaging at 4 and 300 K and by wav

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This work demonstrates the validity of approximating cathodoluminescence generation throughout the electron interaction volume by the total electron energy loss profile. The energy loss profiles in multilayer specimens were accurately calculated using th

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Gas-mediated focused electron beam induced etching (FEBIE) and deposition (FEBID), collectively referred to here as FEBIED, permit nanoscale modification of surface material via chemical reactions involving electron-dissociated precursor molecules. Electrons crossing the solid-vacuum interface usually possess a wide range of energies, are capable of breaking most bonds in typical precursor adsorbates and dissociation products, and can therefore generate a wide range of mobile, chemically active species. Adsorption, desorption, diffusion, and dissociation of these species all contribute to the development of nanostructures fabricated by FEBIED processes. Furthermore, these nanostructures are often electron-sensitive, and thus their structure evolves during deposition. The wide range of processes behind FEBIED yields very complex behavior that is yet to be modeled realistically fifty years after Christy first proposed a simple analytical model of deposition induced by a broad (defocused) electron beam [1]. A complete description of FEBIED requires a realistic model of electron-gas and electron-solid interactions, the spatial and energy distributions of secondary and backscattered electrons, electron interactions with adsorbates, and the behavior of adsorbates and dissociation products at the solid-vacuum interface.

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We demonstrates engineering of quantum emitters in hBN multi-layers using either electron beam irradiation or annealing. The defects exhibit a broad range of multicolor room-temperature single photon emissions across the visible and the near-infrared ranges.

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We present a low vacuum tool for ultra high resolution scanning electron microscopy of insulators and floating conductors. Charging is stabilized by ionized gas molecules generated using an environmental secondary electron detector designed to operate within the magnetic field on an immersion objective lens. The charge stabilization mechanism yields consistent charge control that is transparent to the operator, and independent of the tasks performed during imaging. This is illustrated by series of artifact-free, high resolution images of an insulating test sample acquired as a function of magnification and scan speed, at a number of accelerating voltages. The low vacuum method is compared to the high vacuum technique of adjusting the electron beam landing energy so as to minimize charging artifacts (i.e., the "total yield" method). The low vacuum approach is less sensitive to changes in beam current density (determined by the beam current, magnification, scan speed and beam diameter) and yields higher ultimate image resolution. The resolution improvement results from effective suppression of both charge-induced defocusing of the electron beam and distortion of the scan pattern.

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The deformation behavior of as-grown and ion-beam-modified wurtzite GaN films is studied by nanoindentation with a spherical indenter. Atomic force microscopy (AFM) and cathodoluminescence are used to characterize the deformation mode. No systematic dependence of the mechanical properties on the film thickness (at least for thicknesses from 1.8 to 4 m) as well as on doping type is observed. Results strongly suggest that (i) slips is the major contributor to the plastic deformation of crystalline GaN and (ii) slip nucleation (rather than a phase transformation) is responsible for "pop-in" events observed during loading. Indentation with an 4.2 m radius spherical indenter at maximum loads up to 900 mN does not produce any cracking visible by AFM in crystalline GaN. Instead, under such loads, indentation results in a pronounced elevation of the material around the impression. Implantation disorder dramatically changes the deformation behavior of GaN. In particular, implantation-produced defects in crystalline GaN suppress (i) "pop-in" events during loading, (ii) slip bands observed by AFM, and (iii) the plastic component of deformation. GaN amorphized by ion bombardment exhibits plastic flow even for very low loads. The values of hardness and elastic modulus of amorphous GaN are dramatically reduced compared to those of as-grown GaN.

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The damage build-up and amorphization behavior in wurtzite GaN films under a wide range of implant conditions are studied by Rutherford backscattering / channeling spectrometry, transmission electron microscopy, and cathodoluminescence spectroscopy. A strong surface peak of lattice disorder, in addition to the expected damage peak in the region of the maximum of nuclear energy loss, has been observed for all implant conditions of this study. Capping of GaN with SiOxand SixNylayers prior to implantation does not eliminate surface disordering. This may suggest that nitrogen loss is not the main reason for the observed enhanced surface disorder, but, rather, the GaN surface acts as a strong sink for migrating point defects. However, pronounced loss of N during ion bombardment is observed for high dose implantation when the near-surface region is amorphized. Moreover, after amorphization, annealing at temperatures above about 400 °C leads to complete decomposition of the near-surface layer.

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Artificial atomic systems in solids such as single photon emitters are
becoming increasingly important building blocks in quantum information
processing and scalable quantum nanophotonic networks. Here, we report on a
controllable way to engineer emitters in two-dimensional (2D) hexagonal boron
nitride (hBN) crystals using plasma processing. The method is robust, and
yields a 7-fold increase in the density of emitters in hBN, which is promising
for their deployment in practical devices. While as-fabricated emitters suffer
from blinking and bleaching, a subsequent annealing step yields photo-stable
emitters. The presented process is the first step towards controllable
placement of quantum emitters in hBN for integrated on-chip quantum
nanophotonics based on 2D materials.

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Recent advances in focused ion beam technology have enabled high-resolution,
direct-write nanofabrication using light ions. Studies with light ions to date
have, however, focused on milling of materials where sub-surface ion beam
damage does not inhibit device performance. Here we report on direct-write
milling of single crystal diamond using a focused beam of oxygen ions. Material
quality is assessed by Raman and luminescence analysis, and reveals that the
damage layer generated by oxygen ions can be removed by nonintrusive
post-processing methods such as localised electron beam induced chemical
etching.